US3446584A - Method of production of chlorine dioxide and sodium sulfate - Google Patents

Method of production of chlorine dioxide and sodium sulfate Download PDF

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Publication number
US3446584A
US3446584A US439193A US3446584DA US3446584A US 3446584 A US3446584 A US 3446584A US 439193 A US439193 A US 439193A US 3446584D A US3446584D A US 3446584DA US 3446584 A US3446584 A US 3446584A
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crystallizer
chlorine dioxide
generator
sodium
zone
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US439193A
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Willard A Fuller
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Kemanord AB
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Hooker Chemical Corp
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Assigned to OCCIDENTAL CHEMICAL CORPORATION reassignment OCCIDENTAL CHEMICAL CORPORATION CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). EFFECTIVE APRIL 1, 1982. Assignors: HOOKER CHEMICALS & PLASTICS CORP.
Assigned to KEMANORD AB, STOCKHOLM, SWEDEN A CORP. OF SWEDEN reassignment KEMANORD AB, STOCKHOLM, SWEDEN A CORP. OF SWEDEN ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: OCCIDENTAL CHEMICAL CORPORATION
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B11/00—Oxides or oxyacids of halogens; Salts thereof
    • C01B11/02—Oxides of chlorine
    • C01B11/022—Chlorine dioxide (ClO2)
    • C01B11/023—Preparation from chlorites or chlorates
    • C01B11/025—Preparation from chlorites or chlorates from chlorates without any other reaction reducing agent than chloride ions

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  • This invention relates to the production of chlorine dioxide and the recovery of sodium sulfate. More particularly, this invention relates to a new process for the pro duction of chlorine dioxide from sodium chlorate, chloride ion and sulfuric acid, and to the recover of sodium sulfate salts.
  • the present process eliminates the need for refrigeration, uses less evaporation equipment and effects the recovery of either an anhydrous sodium sulfate or a hydrated sodium sulfate.
  • the capability of recovering an anhydrous sodium sulfate salt is a significant advancement, particularly where much of the previously used elaborate equipment is eliminated.
  • the anhydrous salt is a more desirable product.
  • previous methods produced hydrated sodium sulfate, which requires a dehydration step prior to fitting it for use in many proccesses.
  • a process for the production of chlorine dioxide and sodium sulfate comprising reacting in a generator zone at an acidity of more than 4.3 normal, an aqueous solution of sodium chlorate and a reducing agent, thereby generating gaseous chlorine dioxide and chlorine, withdrawing liquid effluent from said generator zone, passing said liquid efiluent to a crystallizing zone, adding to said liquid effluent replenishing amounts of aqueous sodium chlorate-reducing agent solution and further reacting said replenished solution to produce chlorine dioxide and chlorine, thereby reducing the acid normality in the crystallizer zone to less than 4.3 normal, maintaining the crystallization Zone under a reduced pressure to effect removal of produced chlorine dioxide, chlorine and water vapor, thereby effecting the concentration of sodium ions and sulfate ions to precipitate sodium sulfate.
  • this process is preferably conducted continuously by removing sodium sulfate crystals from the crystallizer liquor and returning the mother liquor to the generator zone.
  • the present process provides a continuous method of generating chlorine dioxide and chlorine in both the generator and the crystallizer, the process being effected in two distinct stages, that is, the production of chlorine dioxide and chlorine in the generation zone under high acid normalities, and the production of chlorine dioxide and chlorine and in the crystallizer zone under lesser acid normalities and high vacuum.
  • a highly economical chlorine dioxide production method is provided wherein either anhydrous and/or hydrated sodium sulfate is produced as a by-product in the crystallizing zone and wherein crystallization is effected at temperatures about the same as those utilized in the generator zone.
  • the present process effects a change in acid normality in the crystallizer zone, from that present in the generator zone, by dilution with replenishing amounts of aqueous sodium chlorate-chloride solution and by permitting continuation of the chlorine dioxide reaction, thereby further reducing the hydrogen ion concentration in the crystallizer.
  • This eliminates the need for the addition of large quantities of Water as previously required in chlorine dioxide-sodium sulfate crystallization processes which, in turn, further diluted the sodium ion and sulfate ion concentration in the crystallizer, thus requiring crystallization temperatures below zero degree centigrade.
  • the higher crystallizer operating temperature enables operation of the crystallizer at or near the boiling temperature of the chlorate solution under reduced pressure.
  • Crystallizer 14 is operated under a vacuum of about 5 millimeters to about 350 millimeters of mercury, and preferably about 100 millimeters to about 250 millimeters of mercury.
  • the temperature is retained near or at the boiling point of the reaction mixture in accordance with the reduced pressure.
  • the temperature is maintained in the range of about degrees centigrade to about SOdegrees centigrade, and more preferably in the range of about degrees centigrade to about degrees centigrade.
  • large quantities of water are volatilized from the crystallizer and removed via line 12 with the chlorine dioxide and chlorine generated in the crystallizer.
  • the acid normality of the solution in the crystallizer is maintained at less than about 4.3 normal, and preferably between about 2.5 and 4.3 normal. Under such acidic conditions, temperatures and the presence of the added sodium chlorate-chloride solution, chlorine dioxide and chlorine are produced. The amount of chlorine dioxide produced is dependent to a large extent on the solution concentration, temperature and acidity. More chlorine dioxide and chlorine are produced at the higher acid normalities and the warmer temperatures.
  • Crystallizer 14 is supplied with heat by either external or internal heating, using either direct or indirect heating means or heat transfer agents, such as steam, hot water or other conventional heating methods.
  • Various crystallizers can be used such as those having a vacuum flashing zone, either apart from the main crystallizing zone with circulation between the flashing Zone and the crystallizing zone, or total vacuum evaporators, as well as various other crystallizers having circulation methods and flow patterns conventional to the crystallizing art.
  • suitable crystallizers are those which are capable of operating under vacuums corresponding to the solution boiling points at temperatures ranging from about 20 degrees centigrade to about degrees centigrade.
  • the sodium chlorate-chloride solution added to the crystallizer is an aqueous solution of sodium chlorate containing chloride ion at a concentration such that a ratio of about 0.1 mole to about 1.2 moles chloride ion per mole of sodium chlorate results in the crystallizer solution.
  • the sodium chlorate-chloride concentration ratio in the crystallizer is at about an equimolar ratio.
  • additional reducing agents other than the chloride are used, less than about the equimolar ratio of chloride to chlorate is used.
  • the chloride ion added to the crystallizer may be added as sodium chloride or hydrochloric acid.
  • the particular chloride ion used and the decision of whether to supplement the chloride ion with a reducing agent other than a chloride, are based upon the particular availability of hydrochloric acid and sodium chloride, the economic conditions, as well as the particular demand for sodium sulfate and chlorine.
  • another reducing agent such as sulfur dioxide
  • lesser amounts of sodium sulfate and chlorine are recovered from the process.
  • hydrochloric acid is used as a partial or complete replacement for the sodium chloride, the lesser amounts of sodium ion present result in a lesser recovery of sodium sulfate.
  • the exact feed solutions can be varied considerably with varying production requirements.
  • chlorate cell liquor is a desirable source of sodium chlorate and sodium chloride.
  • Cell liquor is readily adjusted to most ratios of chlorate to chloride.
  • cell liquor containing 300 grams to about 700 grams per liter sodium chlorate and about 20 grams to about 200 grams per liter sodium chloride can be used.
  • Crystallizer solution containing precipitated sodium sulfate is continuously removed from crystallizer 14 via line 18 where it is passed through filter 20 prior to being routed via lines 22 and 30 to generator 24.
  • mother liquor from filter 20 can be returned to crystallizer 14 and efiiuent liquor decanted from crystallizer 14 can be fed to generator 24.
  • sodium sulfate is removed from the crystallizer solution and washed with water prior to being removed from filter 20 via line 26. Wash water, which is passed through filter 20, is returned in whole or in part to crystallizer 14 via line 28, as required. In normal operations, little or no water, in addition to the chlorate-chloride solution, is required in the crystallizer.
  • the crystallizer liquor, passing through filter 20, is subsequently fed to generator 24.
  • This feed preferably enters generator 24 countercurrently to the efiiuent gases from the generator.
  • Generator 24 operates under acidic conditions greater than those existing in the crystallizer. Therefore, additional quantities of sulfuric acid are added to generator 24 either directly or in admixture with the mother liquor from crystallizer 14 as via line 32.
  • Sufficient sulfuric acid or acidic sulfate solutions from other generators is added to the generator so as to increase the acid normality of the generator liquor above 4.3 normal and preferably, to increase the acid normality to about 8 to about 12 normal. Concentrated sulfuric acid, e.g., percent to 98 percent, is conveniently used.
  • Generator 24 can be operated as a conventional chlorine dioxide generator at about atmospheric pressure using an inert gas sweep, such as air, to aid in the removal and dilution of the chlorine dioxide produced from generator 24- via line 30.
  • generator 24 can also be maintained under a vacuum of about 5 millimeters to about 350 millimeters of mercury or substantially equal to the vacuum maintained in the crystallizer.
  • This Water is conveniently removed by vacuum operation.
  • an inert gas purge is not required to effect the removal of generated chlorine dioxide and chlorine and to effect dilution.
  • Generator 24 is supplied with heat by either external or internal heating using either direct or indirect heating means or heat transfer agents such as steam, hot water and other conventional heating methods. Also, various water evaporation methods can be used such as a vacuum flashing zone, either apart from the main generating zone with circulation between the flashing zone and the generator zone, or total vacuum evaporators, as well as various other generators having circulation methods and flow patterns conventional to chlorine dioxide generation.
  • reducing agents can be used to supplement the reaction.
  • reducing agents as sulfur dioxide, methanol, formaldehyde, formic acid, and the like, are conveniently used.
  • Effluent liquor from generator -24 is continuously withdrawn and returned to crystallizer 14 via line 34.
  • the generator liquid effluent provides the feed of sulfate ions to the crystallizer wherein they are subsequently removed from the system by crystallization as sodium sulfate.
  • Chlorine dioxide, chlorine, and water vapor are fed to absorption means 16.
  • EXAMPLE 1 The process of the present invention is effected as illustrated in the drawing to produce chlorine dioxide wherein about 50 percent of the chlorine dioxide is produced in the crystallizer and the remaining 50 percent of the chlorine dioxide is produced in the generator.
  • An aqueous solution of 38.0 parts per minute of water, 16.6 parts per minute of sodium chlorate and 9.5 parts per minute of sodium chloride is fed to a vacuum crystallizer countercurrently to the gases being evolved from the crystallizer.
  • the vacuum crystallizer has heating means for retaining the solution at the desired temperature under the vacuum conditions.
  • Eflluent liquor from a generator zone is also fed to the crystallizer in an amount which comprise 13.2 parts per minute of sulfuric acid, 12.7 parts per minute of sodium sulfate and 15.1 parts per minute of water.
  • the mixed feed streams result in an acid normality of about 4.2 normal in the crystallizer.
  • the crystallizer is maintained under a vacuum of about 200 millimeters of mercury and a temperature of about 65 degrees centigrade. Under these conditions, chlorine dioxide and chlorine are evolved in an amount of 5 parts per minute of chlorine dioxide and 2.5 parts per minute of chlorine in admixture with 41.3 parts per minute of water.
  • Efiluent liquor from a settling zone in the crystallizer zone is continuously withdrawn and passed through a filter wherein 23.2 parts per minute of anhydrous sodium sulfate are removed. The filtrate is subsequently returned to the crystallizer.
  • a second effluent stream is continuously withdrawn from another portion of the crystallizer and fed to a generator.
  • the generator is suitable for vacuum operation and has heating means for sustaining the desired temperature under the vacuum conditions.
  • the effluent liquor from the crystallizer which is fed to the generator zone contains about 4.2 moles per liter of hydrogen ion, 7.45 moles per liter of sodium ion, 2.76 moles per liter of sulfate ion, 3.13 moles per liter of chloride ion and 3.0 moles per liter of chlorate ion in aqueous solution.
  • 16.3 parts per minute of 98 percent sulfuric acid are fed to the generator.
  • the generator is operated at a temperature of about 71 degrees centigrade under a vacuum of about 200 millimeters of mercury. Chlorine dioxide and chlorine are evolved from the generator in an amount of 5 parts per minute of chlorine dioxide and 2.5 parts per minute of chlorine in admixture with 1.7 parts per minute of water.
  • the continuous operation of the crystallizer and generator effects the produtcion of parts per minute of chlorine dioxide and 5 parts per minute of chlorine in admixture with 43 parts per minute of water. Also produced as a by-product are 23.2 parts per minute of anhydrous sodium sulfate.
  • EXAMPLE 2 A mixture of chlorine dioxide and chlorine is produced by the method of this invention wherein about 50 percent of the chlorine dioxide is produced in the crystallizer and the remaining 50 percent is produced in the generator. This example further illustrates chlorine dioxide production at a rate similar to that of Example 1, wherein less sodium sulfate is produced by utilizing an additional reducing agent to supplement the chloride reducing agent.
  • An aqueous solution of 31.8 parts per minute of water, 16.6 parts per minute of sodium chlorate and 6.5 parts per minute of sodium chloride is fed to a crystallizer similar to that of Example 1, in addition to liquid efiluent from a generator zone which comprises about 9.0 parts per minute of sulfuric acid, 9.9 parts per minute of sodium sulfate and 10.3 parts per minute of water.
  • the mixing of these feed solutions in the crystallizer effects the production of chlorine dioxide and chlorine, which further reduce the acid normality of the solution in the crystallizer so as to result in an acidity of about 4.2 normal.
  • the crystallizer is maintained at a temperature of about 60 degrees centigrade under a vacuum of about 150 millimeters of mercury. Under the conditions of acidity, temperature and the chlorate and chloride ion concentration, 5- parts per minute of chlorine dioxide, 2.5 parts per minute of chlorine and 33.6 parts per minute of water are evolved from the crystallizer. The removal of large quantities of water from the crystallizer, the chlorine dioxide production, and the sodium chlorate-chloride replenishment, increases the concentration of sodium ions and sulfate ions, thereby effecting the crystallization of sodium sulfate.
  • Liquid efiiuent, from the crystallizer, is continuously removed, thereby removing a mixture of crystallized sodium sulfate and mother liquor.
  • the sodium sulfate crystals are removed from solution by passing through a filter.
  • the mother liquor is subsequently passed to the generator. In this manner, 18.9 parts per minute of anhydrous sodium sulfate are recovered from the crystallizer.
  • the mother liquor removed from the crystallizer has a concentration of about 4.2 moles per liter of hydrogen ion, 7.52 moles per liter of sodium ion, 2.76 moles per liter of sulfate ion, 1.7 moles per liter of chloride ion and 4.5 moles per liter of chlorate ion.
  • This solution is mixed in a generator similar to that of Example 1, with 10.8 parts per minute of concentrated sulfuric acid.
  • the acid addition increases the normality of the solution in the generator to about 10 normal.
  • Also fed to the generator are 1.1 parts per minute of sulfur dioxide, which provides an additional reducing agent for the sodium chlorate.
  • the generator is maintained at a temperature of about 66 degrees centigrade under a pressure of about 150 milliliters of mercury.
  • the conditions of temperature, acidity and chlorate ion concentration effect the production of chlorine dioxide and chlorine in an amount of 5 parts per minute of chloride dioxide and 1.8 parts per minute of chlorine, while effecting the removal of 1.7 parts per minute of water.
  • the present invention is also readily effected by operating the crystallizer zone at acid normalities between about 2.5 and 4.3 normal, and at temperatures ranging from about 20 degrees centigrade to about degrees centigrade with vacuums sufiiciently high at the given temperature to effect a high vapor pressure in the crystallizer. Also, by operating the crystallizer at the lower temperatures, hydrated sodium sulfate can be produced.
  • the generator zone can be operated at acid normalities other than those of Examples 1 and 2, especially those ranging from 4.3 up to about 12 normal, and preferably between about 8 and 12 normal.
  • Inert gases other than air can also be used to sweep the generator and aid in the dilution of the produced chlorine dioxide.
  • a process for the production of chlorine dioxide and sodium sulfate comprising:
  • a process for the continuous production of chlorine dioxide and sodium sulfate comprising reacting in a generator zone at an acidity of 8 to about 12 normal, an aqueous solution of sodium chlorate and a chloride selected from the group consisting of sodium chloride and hydrochloric acid, at a temperature of 20 degrees centigrade to 70 degrees centigrade, thereby generating gaseous chlorine dioxide and chlorine, withdrawing liquid efiiuent from said generator zon'e, passing said liquid eflluent to a crystallizing zone, adding to said liquid effluent replenishing amounts of aqueous sodium chlorate-chloride solution, and further reacting said replenished solution to produce chlorine dioxide and chlorine thereby reducing the acid normality in the crystallizer zone to about 2.5 to 4.3 normal, maintaining the crystallizer zone at a temperature of about 20 degrees centigrade to 80 degrees centigrade and under a vacuum sufficient to effect the removal of water vapor, thereby effecting the concentrating of sodium ions and sulfate ions and thereby
  • a process for the continuous production of chlorine dioxide and sodium sulfate comprising reacting in a generator zone at an acidity of about 8 to 12 normal under vacuum of 5 millimeters to 350 millimeters of rrrercury, an aqueous solution of sodium chlorate and a reducing agent selected from the group consisting of sodium chloride, hydrochloric acid, sulfur dioxide, and mixtures thereof, at a temperature of 20 degrees centigrade to 70 degrees centigrade, thereby generating gaseous chloride dioxide and chlorine, withdrawing liquid eflluent from said generator zone, passing said liquid effiuent to a crystallizer zone, adding to said liquid eflluent replenishing amounts of aqueous sodium chloride and reducing agent, further reacting said replenished solution to produce chlorine dioxide and chlorine thereby reducing the acid normality in the crystallizer zone to about 2.5 to 4.3 normal, maintaining the crystallizer zone at a temperature of about 35 degrees centigrade to 70 degrees centigrade and a vacuum of 1 00 millimeter
  • a process for the continuous production of chlorine dioxide and sodium sulfate comprising reacting in a generator zone at an acidity of 8 to about 12 normal an aqueous solution of sodium chlorate and a chloride selected from the group consisting of sodium chloride and hydrochloric acid at a temperature of 20 degrees centigrade to 70 degrees Centigrade, thereby generating gaseous chlorine dioxide and chlorine; with-drawing liquid effluent from said generator zone; passing said liquid efiluent to a crystallizing zone; adding to said liquid efliuent replenishing amounts of aqueous sodium chlorate-chloride solution; further reacting said replenished solution to produce chlorine dioxide and chlorine, thereby reducing the acid normality in the crystallizer zone to about 2.5 to 4.3 normal; maintaining the crystallizer zone at a temperature of about 20 degrees centigrade to 80 degrees centigrade; and maintaining both the generator and crystallizer zones under vacuums sufficient to effect the removal of Water vapor, the vacuums in said zones being substantially the same, thereby eifect

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
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  • Inorganic Chemistry (AREA)
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US439193A 1965-03-12 1965-03-12 Method of production of chlorine dioxide and sodium sulfate Expired - Lifetime US3446584A (en)

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US (1) US3446584A (sk)
DE (1) DE1274565B (sk)
FI (1) FI45036C (sk)
GB (1) GB1123871A (sk)
NO (1) NO116964B (sk)
SE (1) SE329386B (sk)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3864457A (en) * 1972-12-22 1975-02-04 Ppg Industries Inc Process for the production of chlorine dioxide
US3929974A (en) * 1970-06-10 1975-12-30 Erco Ind Ltd Production of chlorine dioxide
US4206193A (en) * 1978-12-18 1980-06-03 Hooker Chemicals & Plastics Corp. Versatile process for generating chlorine dioxide
US4483740A (en) * 1983-08-03 1984-11-20 A. H. Lundberg Associates, Inc. Method for recovery of reusable chemicals from C102 generator effluent
US10266406B1 (en) * 2018-05-18 2019-04-23 Guangxi University Producing high-purity chlorine dioxide gas
CN109704282A (zh) * 2019-01-30 2019-05-03 广东至诚紫光新材料有限公司 用于除甲醛的二氧化氯溶液及其制备方法、应用

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1136378A (en) * 1979-05-31 1982-11-30 Gerald Cowley Small scale chlorine dioxide plant
SE465569B (sv) * 1989-04-18 1991-09-30 Eka Nobel Ab Foerfarande foer framstaellning av klordioxid

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2811420A (en) * 1954-11-17 1957-10-29 Hooker Electrochemical Co Chlorine dioxide generation
US3341288A (en) * 1963-12-27 1967-09-12 Hooker Chemical Corp Production of chlorine dioxide

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE858997C (de) * 1947-01-14 1952-12-11 Mo Och Domsjoe Ab Verfahren zur Herstellung von Chlordioxyd
DE1051256B (de) * 1957-11-09 1959-02-26 Hoechst Ag Verfahren zur kontinuierlichen Herstellung von Chlordioxyd

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2811420A (en) * 1954-11-17 1957-10-29 Hooker Electrochemical Co Chlorine dioxide generation
US3341288A (en) * 1963-12-27 1967-09-12 Hooker Chemical Corp Production of chlorine dioxide

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3929974A (en) * 1970-06-10 1975-12-30 Erco Ind Ltd Production of chlorine dioxide
US3864457A (en) * 1972-12-22 1975-02-04 Ppg Industries Inc Process for the production of chlorine dioxide
US4206193A (en) * 1978-12-18 1980-06-03 Hooker Chemicals & Plastics Corp. Versatile process for generating chlorine dioxide
US4483740A (en) * 1983-08-03 1984-11-20 A. H. Lundberg Associates, Inc. Method for recovery of reusable chemicals from C102 generator effluent
US10266406B1 (en) * 2018-05-18 2019-04-23 Guangxi University Producing high-purity chlorine dioxide gas
CN109704282A (zh) * 2019-01-30 2019-05-03 广东至诚紫光新材料有限公司 用于除甲醛的二氧化氯溶液及其制备方法、应用
CN109704282B (zh) * 2019-01-30 2022-05-27 广东至诚紫光新材料有限公司 用于除甲醛的二氧化氯溶液及其制备方法、应用

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DE1274565B (de) 1968-08-08
SE329386B (sk) 1970-10-12
FI45036B (sk) 1971-11-30
GB1123871A (en) 1968-08-14
FI45036C (fi) 1972-03-10
NO116964B (sk) 1969-06-16

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